1. Field of the Invention
This invention relates to mixed-solid solution tri-metallic oxide/sulfide catalysts useful for removal of at least one of sulfur, nitrogen and oxygen from hydrocarbon liquids. The active metallic catalyst is in oxide or sulfide form and mixed with a solid solution substrate of at least two metallic oxides. The catalysts are stable and active under high temperature conditions and are tolerant to sulfur containing feed materials. Removal of at least one of sulfur, nitrogen and oxygen from hydrocarbon liquids is achieved by contacting the hydrocarbon liquids with CO, CO.sub.2, and C.sub.1 to C.sub.4 hydrocarbons in the presence of a mixed-solid solution tri-metallic oxide/sulfide catalyst.
2 Description of the Prior Art
Specific metal oxides and metal sulfides and mixtures of metal oxides and metal sulfides are known to serve as catalysts, particularly for low temperature hydrogenation reactions. Several U.S. Patents teach molybdenum sulfide catalysts and their use in methanation and hydrotreating processes: U.S. Pat. No. 4,431,747 teaching carbon containing molybdenum and tungsten sulfide catalysts; U.S. Pat. No. 4,666,878 teaching iron promoted molybdenum and tungsten sulfide catalysts; and U.S. Pat. Nos. 4,595,672 and 4,698,145 teaching promoted molybdenum and tungsten sulfide catalysts for hydroprocessing. U.S. Pat. No. 3,116,345 teaches a catalyst for hydroisomerization which is a sulfide of one or more metals of chromium, molybdenum, and tungsten and/or a sulfide of one or more metals of iron, cobalt and nickel on a solid support of silica, alumina, or mixed silica-zirconia. U.S. Pat. Nos. 4,243,553 and 4,243,554 teach molybdenum disulfide catalysts for hydrodenitrogenation and hydrodesulfurization. U.S. Pat. Nos. 4,151,191 and 4,260,553 teach mixed metallic catalysts of molybdenum oxides or sulfides, lanthanide and actinide oxides or sulfides; and aluminum, tungsten and silicon oxides may be used as methanation catalysts up to about 600.degree. C. U.S. Pat. Nos. 4,320,030 and 4,491,639 teach vanadium, molybdenum or tungsten sulfide or mixed sulfide/oxide compounds which may contain aluminum, silicon, boron, cerium or titanium; cobalt, nickel, iron or manganese; carbon; and nitrogen for use as hydrogenation catalysts.
The applicants do not have knowledge of any tri-metallic oxide/sulfide catalysts wherein a first metallic oxide/sulfide is mixed with a solid solution of a second and third metallic oxide material. The applicants do not have knowledge of processes for catalytic removal of sulfur, nitrogen and/or oxygen from hydrocarbon liquids in the presence of a mixed-solid solution tri-metallic oxide/sulfide catalyst and a gaseous carbon-containing compound wherein hydrogen is present in only incidental amounts, certainly not in amounts to substantially effect hydrogenation reactions as taught by the prior art.